Process for bi-organic peroxides

ABSTRACT

An aliphatic or cycloaliphatic hydroperoxide, an olefin such as a 1-aromatic-1-substituted ethylene and a halide corresponding to the ethylene are reacted under essentially anhydrous conditions, in the absence of a free acid, at a temperature below the decomposition temperature of the halide to obtain a peroxide corresponding to the hydroperoxide and the ethylene. 
     Preferably the product peroxide is recovered by treating the reaction product mixture with aqueous alkali metal hydroxide to destroy the halide and hydroperoxide therein; then distilling the treated mixture in the presence of a substantial amount of liquid water at sub-atmospheric pressure to remove overhead impurities. 
     Example: Dicumyl peroxide is prepared by reacting at about 30° C for about 5 hours cumene hydroperoxide, α-methylstyrene and cumyl chloride, which compounds has been charged to the reaction zone in a mole ratio of 1.25: 0.86: 0.14 and treating the reaction product mixture with aqueous alkali metal hydroxide to remove cumyl chloride and cumene hydroperoxide to obtain a product mixture including dicumyl peroxide; and adding 2-10 parts of liquid water to the product mixture in a distillation zone and vaporizing water and impurities at a temperature of about 30-80° C at a pressure of about 0.01-0.5 atmospheres and continuing said vaporization until essentially no oily liquid is obtained in a condensor receiving vapors from said zone, under conditions such that a substantial amount of liquid water is present in said zone in contact with peroxide product.

BACKGROUND OF THE DISCLOSURE

1. Field of the Invention.

This invention relates to organic peroxides, such as dicumyl peroxide.More particularly, the invention relates to the preparation of suchorganic peroxides and also to the purification thereof.

2. Description of the Prior Art.

Extensive prior art exists on the preparation of aralkyl and alkylperoxides. The prior art can best be summarized under three majormethods of preparation.

1. The acid-catalyzed condensation of a hydroperoxide with an alcohol[Milas and Harrris, JACS, 60, 2434 (1938); Milas and Surgenor, JACS, 68,205 (1946); Milas and Perry, JACS, 68, 1938 (1946); U.S. Pat. Nos.2,668,180 (1954), 3,254,130 (1966), 3,310,588 (1967); and 3,337,639(1967).] This is probably the most widely known and widely used methodfor the preparation of alkyl peroxides. This method is best used wherethe product peroxide is not acid-sensitive, where the hydroperoxide isrelatively stable to acid, and where the alcohol is tertiary and readilyforms a carbonium ion. This method is less satisfactory when one or moreof the above conditions are not met. For example, the acid-sensitivityof cumene hydroperoxide is widely known. Cumyl t-butyl peroxide can beprepared in good yield by the sulfuric acid catalyzed condensation ofcumyl alcohol and t-butyl hydroperoxide but can not be prepared by thesulfuric acid catalyzed condensation of cumene hydroperoxide and t-butylalcohol. Peroxides containing an aralkyl group are also somewhatacid-sensitive although to a much less degree than cumene hydroperoxide.Thus, dicumyl peroxide and cumyl t-butyl peroxide will decompose in thepresence of mineral acids even at room temperature giving among otherthings phenol and acetone. Several patents (see list above) teach thepreparation of dicumyl peroxide by the acid-catalyzed condensation ofcumene hydroperoxide and cumyl alcohol; we have found such processes tobe unsatisfactory and very hazardous.

2. The acid-catalyzed addition of a hydroperoxide to an olefin [Milasand Harris; Milas and Surgenor; Davies et al., J. Chem. Soc., 2200(1954) and U.S. Pat. No. 3,267,066 (1967)].

This process has the same advantages and disadvantages of (1) above. Itis generally used with olefins which readily form tertiary carboniumions such as the acid-catalyzed addition of t-butyl hydroperoxide toisobutylene or diisobutylene. It is less satisfactory for olefins likeα-methylstyrene which readily undergo acid-catalyzed telomerization.U.S. Pat. No. 3,267,066 shows the preparation of dicumyl peroxide fromα-methylstyrene, cumene hydroperoxide and hydrogen chloride.

3. The displacement reaction between an alkali metal salt of ahydroperoxide and an alkyl halide [U.S. Pat. No. 2,403,709 (1946), T. W.Campbell and G. M. Coppinger, J. Am. Chem. Soc., 73 1789 (1951), andU.S. Pat. No. 3,247,259 (1966).] This is an especially good method forthe preparation of peroxides from primary or secondary halides orsulfates but is of dubious value for tertiary halides sincedehydrohalogenation is far more rapid than the displacement reaction.

4. There are several processes for the preparation of specificperoxides. Dicumyl peroxide is formed as a minor byproduct of theautoxidation of cumene to cumene hydroperoxide. It is not a practicalprocess for the preparation of dicumyl peroxide but represents aby-product of large scale producers of phenol from cumene.

Another method of preparation of aralkyl peroxides is the copperion-catalyzed decomposition of hydroperoxides in the presence ofsubstrates. Thus cumyl t-butyl peroxide (60% yield) can be prepared byheating at 67° for 18 hours a mixture of cumene, t-butyl hydroperoxideand cuprous chloride. However, the stoichiometry requires theconsumption of two moles of hydroperoxide for each mole of peroxideproduced. Thus only 30% of the hydroperoxide is converted to peroxide inthis reaction.

PURIFICATION

At this time the art utilizes two methods for the purification ofaralkyl peroxides, namely, low temperature crystallization or vacuumdistillation; U.S. Pat. Nos. 2,668,180; 3,254,130; 3,310,588; 3,267,066;and 2,691,683 (1954).

Crude dicumyl peroxide is purified by cooling the reaction mixture to-10° C. and allowing crystallization to occur. However, this gives anoily solid which then must be recrystallized from a suitable solventsuch as methanol. In addition, unless the crude mixture contains atleast 75% dicumyl peroxide, crystallization will not take place. Thushigh assay cumene hydroperoxide is needed as starting material.

The other method for purifying dicumyl peroxide consists of distillingimpurities by heating the crude peroxide at 90°-110° under high vacuumfor several hours. The hazards of heating peroxides at thesetemperatures and the necessity of a high vacuum make this processcommercially unattractive. This distillation can give a product assayingabout 90% but it has a dark amber color and must be decolorized andrecrystallized to be acceptable commercially; also these products may gooff color in ordinary storage.

OBJECTS

The main object of the invention is a process for the preparation ofcertain peroxides, especially acid-sensitive peroxides, by a procedurethat does not use a free-acid catalyst.

Another object of the invention is a purification procedure for certainperoxides which produces colorless product by a vaporization operationthat does not require excessively high temperatures.

Other objects will become apparent in the course of the detaileddescription of the invention.

SUMMARY OF THE INVENTION

A. The peroxide preparation process of the invention comprises:

(1) reacting a hereinafter defined olefin, a reactive organic halide,and organic hydroperoxide, in the absence of a free acid, underessentially anhydrous conditions, at a temperature below the temperatureat which substantial decomposition of said organic halide occurs, where

(2) said olefin has the general formula ##STR1## where (a) y is aninteger equal to 1, 2 or 3;

(b) R¹ is an aromatic radical;

(c) R² and R³ are each H, aliphatic, cycloalihatic, or aromaticradicals;

(d) R⁴ is an aliphatic or aromatic radical;

(e) ═CR² R³ may be a cyclic group; ##STR2## may be a cyclic group;##STR3## may be a fused ring group; ##STR4## may be a fused ring grouphaving the C═C portion as a part of the fused ring; and

(i) when R¹ is substituted on more than one ring carbon atoms, only onering carbon atoms ortho to a ##STR5## group may be joined to asubstituent group;

(3) said reactive organic halide has the general formula ##STR6## whereX is I, Br, Cl, or F; and

(4) said organic hydroperoxide has the general formula

    R.sup.5 -[OOH].sub.y

where R⁵ is an aliphatic or cycloaliphatic radical.

B. The preferred preparation process of the invention comprises:

(1) reacting a hereinafter defined olefin, a reactive organic halide,and organic hydroperoxide, in the absence of a free acid, underessentially anhydrous conditions, where

(2) said olefin has the general formula ##STR7## where (a) y is aninteger equal to 1, 2, or 3;

(b) R¹ is phenyl, a fused benzene ring group having 2-3 rings, or adoubled benzene ring group;

(c) R² and R³ are each H, alkyl, cycloalkyl, phenyl, or a correspondinghalo substituted radical;

(d) R⁴ is alkyl, cycloalkyl, phenyl, or a corresponding halo substitutedradical; and

(e) ═CR² R³ may be a cyclic group; ##STR8## may be a cyclic group;##STR9## may be a fused ring group; ##STR10## may be a fused ring grouphaving the C═C portion as a part of the fused ring; and

(i) when R¹ is substituted on more than one ring carbon atom, only onering carbon atom ortho to a ##STR11## group may be joined to asubstituent group; (3) said reactive organic halide has the generalformula ##STR12## where X is Br or Cl; (4) said organic hydroperoxidehas the general formula

    R.sup.5 --[OOH].sub.y

where R⁵ is an aliphatic hydrocarbon radical, a cycloaliphatichydrocarbon radical, or the corresponding halo substituted radical;

(5) at a temperature in the range of about 0°-60° C. for a time in therange of about 1-12 hours with the longer times being associated withthe lower temperatures;

(6) the mole ratio of --OOH groups in said hydroperoxide charged to theethylenic bonds in said olefin charged is about 2.0-1.1:1; and

(7) said halide is charged in an amount of about 10-20 mole percentbased on olefin charged.

C. The purification process of the invention is directed to impureorganic peroxides having the general formula ##STR13## said impureperoxide being essentially free of acidic materials and said impuritieshaving an appreciably lower boiling point than said peroxide where saidimpure peroxide is charged along with 2-10 parts by weight of liquidwater, based on said impure peroxide, to a distillation zone; vaporizingwater and impurities at a temperature of about 30°-80° C. at a pressureof about 0.01-0.5 atmospheres and continuing said vaporization untilessentially no oily liquid is obtained in a condensor receiving vaporsfrom said zone, under conditions such that a substantial amount ofliquid water is present in said zone in contact with peroxide product,wherein

(a) Y is an integer equal to 1, 2, or 3;

(b) R¹ is an aromatic radical;

(c) R² and R³ are each H, aliphatic, cycloaliphatic, or aromaticradicals;

(d) R⁴ is an aliphatic or aromatic radical; ##STR14## may be a cyclicgroup; ##STR15## may be a cyclic group; ##STR16## may be a fused ringgroup; and (h) R⁵ is an aliphatic or cycloaliphatic radical.

The purification process is preferred to be used with the productmixture from the preparation process of the invention, which mixture hasbeen treated with aqueous alkali metal hydroxide to remove organichalide and unreacted hydroperoxide.

DESCRIPTION OF THE INVENTION AND EXAMPLES

The peroxide preparation process of the invention requires as necessarycomponents of the feed a particular class of olefins, a particular classof organic halides, and a particular class of organic hydroperoxides.The components of the feed may be charged to the reaction zone in anyorder or may be premixed.

In this process there is no initial rapid reaction or heat build-up.There is no need to moderate the reaction with a solvent or to controlthe reaction rate by slow addition of one of the materials.

In the case of a batch reactor, it is preferred to charge the entirefeed to the reactor before the start of the reaction. In the case of acontinuous reaction system, it is preferred to charge the componentssimultaneously, for example by premixing, to the reaction zone in thedesired proportions.

The reaction may be carried out in the presence of an inert organicsolvent for one or more of the feed components. However, usually thereaction is carried out without using any added solvent.

The reaction is carried out without the use of any added free-acid suchas is conventionally used in the reaction of olefin and hydroperoxide.

The reaction can best be accomplished by having essentially anhydrousconditions in the reaction zone.

It has been observed that the temperature at which substantialdecomposition of the organic halide occurs is the controlling maximumtemperature for the preparation reaction. In general the reaction can becarried out over the range of temperatures of about 0° (zero) - 60° C.When operating with the preferred olefins, halides, and hydroperoxides,it is preferred to carry out the reaction at a temperature in the rangeof about 20°-50° C.

It has been observed that the yield of peroxide product is influenced byboth the temperature at which the reaction is carried out and the timefor which the reaction is permitted to continue. The proportions of thethree components of the feed also has an influence on the yield ofperoxide product. In general, the higher the temperature used, theshorter the times that should be used when attempting to maximize yield-- at a given proportion in the feed.

It is to be understood that each feed, not only in terms of proportionsbut the components which make up the feed, appears to have its owntemperature-time relation for the optimum yield of peroxide product.However, in general, the reaction time is in the range of about 1 hourto about 12 hours, with the shorter times being desirably associatedwith the higher temperatures. At the preferred temperature range ofabout 20°-50° C., the desirable time range is about 2-10 hours.

It has been observed that each combination of feed has a temperature andtime relation which at first causes the yield of peroxide product toincrease and then causes the yield to decrease. For a given feed, at afixed time, the yield reaches a maximum at some temperature; raising thetemperature beyond this level results in a yield decrease. For a givenfeed, at a fixed temperature the yield reaches a maximum at some pointin time; lengthening the time beyond this point results in a yielddecrease.

It is thought that this yield behaviour cannot be explained merely bythermal or chemical decomposition of the organic halide, and/or thehydroperoxide, and/or the peroxide product. Examination of the dataindicates that a complicated combination of factors must be influencingthe course of the reaction.

It is believed that these statements about the influence of feedcomponents, proportions thereof, and temperature and time when takenwith the numerous examples, especially the series of runs in Examples 7,8, and 9, will enable anyone to readily determine for a given feed theoptimum yield conditions.

It is pointed out that the economics of raw materials and process costsmay dictate a different optimum yield than that obtainable when theseeconomic factors are ignored.

In the overall view, the reaction involves the addition of the --OOHgroup from the hydroperoxide to the ethylenic bond of the olefin to forma bridge between the erstwhile olefin and the erstwhile hydroperoxide.Therefore the proportion of olefin to hydroperoxide in the feed must berelated to the reactive portion of the olefin and hydroperoxiderespectively. In general the feed contains the organic hydroperoxide andthe olefin in a mole ratio of --OOH groups contained in thehydroperoxide to reactive ethylenic bonds contained in the olefin on theorder of about 5:1 to 0.5:1 or, in other words, 5-0.5:1.

It has been discovered that when other conditions are fixed, the yieldof peroxide product is increased as the amount of hydroperoxide presentin the feed is increased. It is definitely beneficial to operate with anexcess of hydroperoxide over the theoretical amount needed to react withthe reactive ethylenic bonds. The preferred mole ratio of --OOH groupscharged to reactive ethylenic bonds charged is about 2.0-1.1:1.

To illustrate: The reaction of cumene hydroperoxide and α-methylstyrenerequires theoretically one mole of each component; a ratio of 1:1. Thereaction of t-butyl hydroperoxide and of bis(isopropenyl)benzenerequires two moles of the hydroperoxide for each mole of the biscompound, a mole ratio of 1:1 in terms of --OOH and C═C present.

The presence of the reactive organic halide is essential to the carryingout of the overall reaction between the olefin and the hydroperoxide.Test 10 demonstrates the critical importance of this component. Ingeneral, the feed contains an amount of the halide of about 2-20 molepercent based on the amount of olefin charged. Excessive halide presentappears to have an adverse effect on the yield. When operating with thepreferred proportion of hydroperoxide and olefin, it is preferred to useabout 10-20 mole percent of halide based on the amount of olefincharged.

It has been observed that with the feed: cumene hydroperoxide,α-methylstyrene, and cumyl chloride the best results at any combinationof temperature and time appear to be obtained with a mole ratio of thethree components, in the above order respectively, of about1.25:1.0:0.15.

THE ORGANIC HYDROPEROXIDES

The organic hydroperoxide charged to the preparation process of theinvention has the general formula:

    R.sup.5 --[OOH].sub.y

Preferably R⁵ is an aliphatic hydrocarbon radical, a cycloaliphatichydrocarbon radical, or a corresponding halo substituted radical, i.e.,halo-aliphatic hydrocarbon radical or halo-cycloaliphatic hydrocarbonradical. The term "aliphatic " includes the aromatic substituted openchain hydrocarbon radicals, for example, benzyl and cumyl. The term"cycloaliphatic" includes the aromatic substituted closed chainhydrocarbon radical, such as, phenylcyclohexyl.

Especially preferred R⁵ is lower alkyl, lower alkenyl, lower alkynyl,cycloalkyl, cycloalkenyl, cycloalkyl-lower alkyl, aralkyl, aralkenyl,the corresponding di- and tri-valent radicals, or the corresponding halosubstituted radicals.

Of most interest is the hydroperoxide wherein one peroxy oxygen of --OOHis joined to a tertiary carbon atom of R⁵. This is shown by the formula.##STR17## where: R⁷ and R⁸ are each lower alkyl or cycloalkyl. R⁷ -C-R⁸may be a carbocyclic ring or a heterocyclic ring containing oxygen aspart of the ring. R⁶ is lower alkyl, lower alkenyl, lower alkynyl,cycloalkyl, cycloalkylalkyl, aryl, aryloxy, alkoxy, hydroxyalkyl, or oneof the following radicals shown by structure ##STR18## R⁹ is loweralkyl, cycloalkyl, aryl, aryloxy, alkoxy, halo or nitro. p is an integerfrom 1 to 10.

q is an interger 1 or 2.

r and s are integers from 1 to 5.

Hydroperoxides are illustrated by alkyl hydroperoxides, such as t-butylhydroperoxide, t-amyl hydroperoxide, 1,1,3,3 tetramethylbutylhydroperoxide, 2,5-dimethyl-2,5-dihydroperoxyhexane and2,7-dimethyl-2,7-dihydroperoxyoctane; aralkyl hydroperoxides such ascumene hydroperoxide, cymene hydroperoxide, diisopropylbenzenemonohydroperoxide, diisopropylbenzene dihydroperoxide,3,5-Bis(α-hydroperoxyisopropyl) cumene and 1,3,5 triisopropylbenzenetrihydroperoxide; cycloalkyl hydroperoxides such as decalinhydroperoxide, pinane hydroperoxide, p-menthane hydroperoxide,1-methylcyclohexyl hydroperoxide and 1-methylcyclopentyl hydroperoxide;acetylenic hydroperoxides such as 2-methyl-2-hydroperoxybutyne-3,1-hydroperoxycyclohexylacetylene, 2,5-dimethyl-2,5-dihydroperoxyhexyne-3and 3-methyl-3-hydroperoxypentyne-1 and ether peroxides such as2-methyl-2-hydroperoxytetrahydrofuran,1-methoxy-1-hydroperoxycyclohexane, 2-isoamyloxy-2-hydroperoxypropane,2-methyl-2-hydroperoxytetrahydropyran and 2-hydroperoxytetrahydropyran;hydroxy alkyl by 2,5-methyl-2-hydroxy-5-hydroperoxy hexane. Actually thescope of operable hydroperoxides is broad; acid-sensitive,base-sensitive and normal hydroperoxides can be used in this processsince it is carried out under anhydrous "neutral" conditions.

THE OLEFIN

The olefin charged to the preparation process has the formula: ##STR19##Preferably R¹ is phenyl, a fused benzene ring group having 2-3 rings, ora doubled benzene ring group; R² and R³ are each H, alkyl, cycloalkyl,phenyl, or a corresponding halo substituted radical; and R⁴ is alkyl,cycloalkyl, phenyl, or a corresponding halo substituted radical Thephenyl and naphthalene radical monoolefins are illustrated by theformulas: ##STR20##

It is evident that these monoolefins can be considered as derivatives ofethylene, specifically 1-aromatic-1-substituted ethylenes.

In Formulas I and II there are two ring carbon atoms ortho to theethylenic group. It has been observed that when both of these positionsare substituted, even though one be an ethylenic group, the reactionrate is hindered to such an extent that these compounds must beconsidered ineffective. In the olefins used in the process of theinvention only one ring carbon atom ortho to an ethylenic group may bejoined to a substituent group.

In Formulas I and II the maximum number of R'" groups is 4 and 6respectively. The minimum number is zero (0). Therefore, n is an integerequal to 0-4; and m is an integer equal to 0-6.

When n is 3, R'" may be joined to either R³ or R⁴ to form a fused ringstyrene.

R'" is a substituent radical which does not interfere with the peroxideformation reaction, such as, lower alkyl, cycloalkyl, aryl, alkoxy,aryloxy, halo, nitro, and the corresponding halo substituted radicals.

Illustrative olefins coming within Formulas I and II and also someolefins having two and three ethylenic groups are set out in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Structure I                                                                   R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                            R"'            n Name                                              __________________________________________________________________________    H  H  CH.sub.3                                                                           --             4 α-Methylstyrene                             H  C.sub.2 H.sub.5                                                                  CH.sub.3                                                                           --             4 2-Phenylbutene-2                                  H  H  C(CH.sub.3).sub.3                                                                  --             4 α-t-Butylstyrene                            H  H  C.sub.6 H.sub.5                                                                    --             4 1,1 Diphenylethylene                              CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                           --             4 2-Phenyl-3-methylbutene-2                         H  H  CH.sub.3                                                                           CH.sub.3       3 p,α-Dimethylstyrene                         H  H  CH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                           3 p-Isopropenylcumene                               H  H  CH.sub.3                                                                           C(CH.sub.3).sub.3                                                                            3 p-t-Butyl-α-methylstyrene                   H  H  CH.sub.3                                                                           C.sub.6 H.sub.5                                                                              3 4-Isopropenylbiphenyl                             H  H  CH.sub.3                                                                           Cl             3 p-Chloro-α-methylstyrene                    H  H  CH.sub.3                                                                           Cl             3 m-Chloro-α-methylstyrene                    H  H  CH.sub.3                                                                           F              3 p-Fluoro-α-methylstyrene                    H  H  CH.sub.3                                                                           Cl             2 3,4 Dichloro-α-methyl-                                                  styrene                                           H  H  CH.sub.3                                                                           Br             3 p-Bromo-α-methylstyrene                     H  (CH.sub.2).sub.4                                                                      --             4 1-Phenylcyclohexene-1                             CH.sub.3                                                                         (CH.sub.2).sub.4                                                                      --             4 1-Phenyl-2-methylcyclo-                                                       hexene-1                                          H  (CH.sub.2).sub.3                                                                      --             4 1-Phenylcyclopentene-1                            H  H  CH.sub.3                                                                            ##STR21##     3 p-Diisopropenylbenzene                            H  H  CH.sub.3                                                                            ##STR22##     2 1,3,5 Triisopropenylbenzene                       H  H  CH.sub.3                                                                            ##STR23##     2 1,2,4 Triisopropenylbenzene                       H  H  (CH.sub.2).sub.3    3 1-Methylenetetralin                                   ##STR24##               1-Methylindene                                    H  H  CH.sub.3                                                                            ##STR25##       4-Isopropenyl-α,α,α',α                                ' tetramethylphthalan                             H  H  CH.sub.3                                                                            ##STR26##     3 p,p'-Diisopropenyl- biphenyl                      H  H  CH.sub.3                                                                            ##STR27##     3 p,p'-Diisopropenyl- diphenyl ether                H  H  CH.sub.3                                                                            ##STR28##     3 p,p'-Diisopropenyl- diphenyl methane              Structure II                                                                  H  H  CH.sub.3                                                                           --             6 1-Isopropenyl-                                                                naphthalene                                       H  H  CH.sub.3                                                                           --             6 2-Isopropenyl-                                                                naphthalene                                       __________________________________________________________________________

Aralkenes of Formulas I and II can be prepared by the dehydration of thecorresponding tertiary alcohols or by the vapor phase dehydrogenation ofthe hydrocarbons. For example, α-methylstyrene and p,α-dimethylstyreneare synthesized commercially by the dehydrogenation of cumene andcymene, respectively. The tertiary alcohols are prepared by conventionalorganic synthesis techniques such as the Grignard reaction or thechromic acid oxidation of hydrocarbons. Olefins of interest are theα-methylstyrene and di- and tri(isopropenyl)benzenes.

REACTIVE ORGANIC HALIDE

The reactive organic halide charged to the process of the invention hasthe formula: ##STR29## It is evident that the halides correspond to thedefined olefin to which the elements of HX have been added. It isdesirable that the halide added to the process, as part of the feed,have the same composition as the halide that would be obtained by addingHX to the olefin which is charged as part of the feed.

X is any halogen, i.e., I, Br, Cl, or F. It is preferred to use thebromo or chloro halides.

One or more methods of preparing halides coming within the definitionare known to the art. Anyone of the olefins listed in Table 1 can beconverted directly or indirectly to a halide suitable for use in theprocess of the invention.

DEFINITIONS

In the formulas aliphatic and cycloaliphatic are used in their broadesttechnical meaning; however, it is to be understood that substituentswhich may be present in the aliphatic or cycloaliphatic radical must beinert, i.e., do not interfere with the preparation reaction. Commonlythe aliphatic radical will have 1-36 carbon atoms, usually 1-22, and thecycloaliphatic radical will have 3-12 ring carbon atoms, usually 4-8, ina single ring compound and 5-24 ring carbon atoms, usually 5-12, in adoubled or fused ring radical. It is to be understood that bothaliphatic and cycloaliphatic may be substituted with one or morearomatic groups.

Aromatic is used in its broadest technical meaning and includes a singlebenzenoid ring, doubled (and higher) rings, and fused rings. These maybe substituted with groups which are inert in the process or by one ormore non-aromatic rings, including fused rings. Commonly these arephenyl, naphthyl and biphenyl radicals.

The above definitions are broad and intentionally so because the radicaldefinitions do not affect the general utility of the compounds in thepreparation of the process set forth herein.

A tertiary aliphatic radical is one where the free valence is associatedwith a carbon atom which is joined directly through its other valenceswith three other carbon atoms, for example, a t-butyl radical.

Lower alkyl is intended to have about 1-12 carbon atoms and usually 1-8carbon atoms.

Alkyl, Alkenyl, and Alkynyl: Each group may include 1, 2, or more carbonatoms. Desirably each has 1-22 or 2-22 carbon atoms. Preferably each has1-12 or 2-12 carbon atoms.

It is to be understood that the definitions above apply to all the R'sherein before given for the hydroperoxide, olefin and halide to be usedin the preparation process of the invention.

THE PURIFICATION PROCESS

The peroxide purification process of the invention is directed to animpure peroxide of the structure ##STR30## The process is especiallydirected to impure peroxides which have been prepared by the preferredpreparation process.

The impure peroxide feed to the purification process must be essentiallyfree of acidic materials and the impurities must have an appreciablelower boiling point than the peroxide.

The purification process is described as water vaporization-distillationoperation because the impure peroxide is subjected to distillationconditions in the presence of liquid water, i.e., liquid water ispresent in the distillation zone along with the peroxide throughout thedistillative purification.

In the purification process about 2-10 parts by weight of liquid water,based on the impure peroxide charge, more usually 3-10 parts, arecharged to the distillation zone along with the impure peroxide. Thedistillation is carried out under conditions such that a substantialamount of liquid water is always present therein in contact with theperoxide; even at the completion of the distillation operation.

The water vaporization-distillation is carried out at sub-atmosphericpressure; one which permits distillation of the impurities at atemperature well below the thermal decomposition temperature of theperoxide. In general, this pressure is in the range of about 0.01-0.5atmospheres and commonly with the preferred peroxides from thepreparation process, the pressure is in the range of about 0.1-0.35atmospheres.

The temperature in the distillation zone is maintained below about 80°C.; usually in the range of about 30°-80° C. Preferably the temperatureis held between about 30°-60° C.

The distillation is continued until no "oily" liquid is obtained in acondensate from a condensor which receives vapors from the distillationzone.

When the charge to the vaporization-distillation process is peroxidemade by the preparation process, it is necessary to first remove thehalide and the unreacted hydroperoxide present in the peroxide productmixture from the preparation reaction. This is conventionallyaccomplished by agitating the peroxide reaction product mixture withaqueous alkali metal hydroxide. (This treatment demonstrates that thehalide is present because of the slowness of the reaction of thehydroxide. This treatment converts the halide to the correspondingolefin.)

The hydroxide treated peroxide mixture may be washed with aqueous saltsolution or with ordinary water, before being charged to thevaporization-distillation process.

At the end of the vaporization-distillation, the distillation bottomsconsist essentially of high purity peroxide and liquid water. Fornormally solid peroxides, the bottoms are cooled, with agitation, andthe peroxide rapidly crystallizes out. The solid may be recovered byfiltration or centrifuging, and then air-dried. For normally liquidperoxides, the peroxide phase is decanted or centrifuged away from theaqueous phase. If necessary the liquid peroxide is dried with a suitablesolid desiccant, such as sodium or magnesium sulfate.

For solid peroxides, the process gives a product typically having anassay in excess of 95%. For liquid peroxides, the process gives aproduct typically having an assay in excess of 90%.

The purification process is especially useful with dicumyl peroxide andt-butyl cumyl peroxide prepared by the preparation process because ofthe ease with which the high purity peroxide is recovered as a solidfrom the distillation bottoms.

EXAMPLES

Numerous examples of the preparation process and purification processare hereinafter set forth. (Test 10 is directed to an attempt to makeperoxide directly from hydroperoxide and halide in the absence ofolefin.) It is to be understood that these examples are not limitingwith respect to the scope of the invention.

In the Examples, all yields of peroxide, except where stated otherwise,have been corrected on the basis of the assay of peroxide product.

In the Examples, the yields recorded have been calculated on the basisof the limiting reactant. However, where the hydroperoxide was not thelimiting reactant, the yields were calculated on the basis that all ofthe olefin plus all of the halide could react to give peroxide. Forillustration: In the case of the feed, cumene hydroperoxide (1.25moles), α-methylstyrene (0.86 mole), and cumyl chloride (0.14 mole) thetheoretical yield was considered to be 1.0 mole of peroxide.

If the halide is ignored as a source of peroxide, then the yield figuresgiven herein must be adjusted by the factor (mole of olefin/mole ofolefin + mole of halide). Thus in a run where the reported yield for theabove dicumyl peroxide preparation is 75% the yield based on olefincharged is 87.1%. This is obtained as follows: ##EQU1##

UTILITY

The peroxides produced herein are useful for all purposes in which knownperoxides of this type are used. Examples 13 and 14 demonstrate thepolyethylene cross-linking ability of a number of peroxides produced bythe process of the invention.

EXAMPLE 1 Dicumyl Peroxide

Into a 100 ml. open-top, jacketed reactor was placed 19.2 g. (0.162 m.)of α-methylstyrene, 4.4 g. (0.0285 m.) of distilled cumyl chloride and37 g. (0.20 m.) of 82% assay cumene hydroperoxide. The mixture wasstirred at 40 ± 2° C. for 5 hours. The reaction mixture was cooled to20° and then stirred for 15 minutes with 40 ml. of 20% sodium hydroxidesolution. The aqueous layer was discarded. The washing with caustic wasrepeated twice and the organic layer washed with 50 ml. portions of 20%sodium chloride solution until neutral. The organic layer was added to400 ml. of water and the mixture distilled at 80-90 mm. on a steam bathuntil no further oil came over with the water. The pot residue wasstirred vigorously and cooled to 0° by adding ice.

The colorless dicumyl peroxide which crystallized was collected in aBuchner funnel by filtration, washed with water and then air-dried. Thesolid dicumyl perioxide weighing 35.4 g. assayed 90.8% (corrected yield59.5%) and contained less than 0.5% cumene hydroperoxide.

EXAMPLE 2 Dicumyl Peroxide

A mixture of 182 g. (1.0 m.) of 83.5% cumene hydroperoxide, 101.5 g.(0.86 m.) of α-methylstyrene and 23.8 g. (0.14 m.) of cumyl chloride wasstirred at 40 ± 1° C. for 5 hours (external heat required). The mixturewas cooled to room temperature and washed with three 50 ml. portions of20% sodium hydroxide solution (washing period 5 minutes first wash and10 minutes second and third wash). The organic layer was washed withfive 300 ml. portions of 25% sodium chloride solution.

The wet crude product, weighing 270 g. was mixed with 1 liter of water.The mixture was distilled at 80-90 mm. until no further oil came overinto the distillate.The pot residue consisting of dicumyl peroxide andwater was stirred vigorously while 200 g. of ice was added. Dicumylperoxide crystallized in colorless shiny needles. Yield 173 g.; assay95% (corrected yield 60.0%); hydroperoxide content 1.3%.

The oily material from the distillate weighed 48.5 g. and consisted of26% cumene, 56% α-methylstyrene and lesser amounts of acetophenone andcumyl alcohol. This recovered material was used without purification ina subsequent run from which a 55.1% yield of dicumyl peroxide wasobtained.

EXAMPLE 3 Dicumyl Peroxide

A. A mixture of 37 g. (0.20 m.) of 82% cumene hydroperoxide, 5.45 g.(0.027 m.) of cumyl bromide and 20.4 g. (0.173 m.) of α-methylstyrenewas stirred for 5 hours at 40° C. The product work-up was the same asthat described in Example 1. The yield of dicumyl peroxide was 41 g.,assay 90.8% (corrected yield 68%).

B. Under identical conditions but using cumyl chloride instead of cumylbromide, the yield was 55.8%.

EXAMPLE 4 1,4 Bis[α-(t-butylperoxy)isopropyl] benzene

Recrystallized p-diisopropenylbenzene (13.4 g., 0.086 m.) and 3.2 g.(0.014 m.) of 1,4 bis(α-chloroisopropyl) benzene were dissolved in 50ml. of benzene. To the benzene solution was added 26.25 g. (0.25 m.) of85% t-butyl hydroperoxide [1.45m of --OOH per mole of isopropenyl] andthe resulting mixture stirred for 2.5 hours at 30° C. The reactionmixture was washed with four 50 ml. portions of 10% potassium hydroxidesolution, three 50 ml. portions of water and then dried over magnesiumsulfate. The filtered solution was stripped in vacuo. The product, anoff-white solid, weighed 29.8 g. (85.6% yield) and melted from 69-74° C.Recrystallization from isopropyl alcohol (4 ml. per g. of product)afforded pure white crystalline 1,4 bis[α-(t-butylperoxy)isopropyl]benzene melting at 76-77° C. (Reported m.p. 77°).

At longer reaction times, the yield decreased; 81% (5 hrs. at 30°); 78%(7.5 hrs. at 30°).

When the molar ratios of -OOH to isopropenyl was raised from 1.45 to1.76, the yield increased to 91% of theory.

EXAMPLE 5 A. 4-(α-Chloroisopropyl)α,α,α',α'-tetramethylphthalan##STR31##

Into a 250 ml., jacketed reactor was placed 25.2 g. (0.1 m) of 1,2,4tris(α-hydroxyisopropyl)benzene, 60.8 g. of concentrated hydrochloricacid and 150 ml. of heptane. The mixture was stirred for 71/2 hours at25° C. The aqueous layer was drawn off and discarded. The heptane layerwas dried over magnesium sulfate, filtered and concentrated in vacuo.The residue, gummy solid, weighing 26 g., was dissolved in a smallamount of pentane and cooled to -20° C. A colorless crystalline productwas filtered off and air-dried, yield 14.5 g.; m.p. 77-80°, chlorine(theory) 13.9%, (found) 13.7%. The infra-red spectrum has a moderateC-Cl absorption at 760 cm.⁻², a strong absorption at 890 cm⁻²attributable to the ##STR32## structure, a strong C-O absorption at 1100cm⁻² and no H-O absorption.

B. Using the procedure of Example 1, t-Butylhydroperoxide,4-isopropenyl-α,α,α',α'-tetramethylphthalan and chlorophthalan preparedin A above were reacted and the product 4-[α-(t-butylperoxy)isopropyl]-α,α,α',α' tetramethylphthalan recovered. This assayed 100% ata yield of 87% and had a m.p. of 81-82° C.

EXAMPLE 6

Numerous other peroxides were made according to one or another of theearlier examples. These peroxides and the corrected yield are listedbelow.

    ______________________________________                                                                    Corr.                                             Peroxide                    Yld %                                             ______________________________________                                        1.   1-(2-Naphthyl)-1-methylethyl t-butyl                                                                     68.                                           2.   2-Phenyl-4-Methyl-2-pentyl t-butyl                                                                       54.                                           3.   1,1-diphenylethyl t-butyl  58.                                           4.   p-t-Butylcumyl t-butyl     57.                                           5.   1,3,5-Tris[α-(t-butylperoxy)isopropyl]benzene                                                      81.5                                          6.   1-Phenylcyclohexyl t-butyl 10.                                           7.   1-(4-biphenyl)-1-methylethyl t-butyl                                                                     20.                                           8.   p-Methylcumyl cumyl        78.                                           9.   p-Isopropylcumyl cumyl     98.5                                          10.  p-t-Butylcumyl cumyl       85.8                                          11.  α-t-Butyl-α-methylbenzyl cumyl                                                               30.                                           12.  t-Butyl p-methylcumyl      55.                                           13.  t-Butyl p-isopropylcumyl   90.                                           14.  p-Chlorocumyl cumyl        64.                                           15.  m-Chlorocumyl cumyl        49.                                           16.  p-Fluorocumyl cumyl        76.                                           ______________________________________                                    

EXAMPLE 7 Effect of Feed Proportions on Peroxide Yield

The effect of feed proportions charged to the reactor on the yield ofdicumyl peroxide (DCP) is demonstrated by the following series of runs,each series was carried out according to the procedure of Example 1 at afixed temperature-time relation, while the proportions of cumenehydroperoxide (CHP), α-methylstyrene (MeS), and cumyl chloride (CX) werevaried from run to run. The results of these two series are set outbelow.

    ______________________________________                                        Temp    Time     CHP     MeS   CX    DCP                                      ° C                                                                            Hours    mole    mole  mole  % Yield (1)                              ______________________________________                                        40      2.5      1.0     1.72  0.28  52.3                                     40      2.5      1.0     1.22  0.28  56.4                                     40      2.5      1.0     0.82  0.28  58.5                                     40      2.5      1.0     0.72  0.28  59.4                                     40      2.5      1.5     0.72  0.28  64.7                                     30      5.0      1.0     0.86  0.14  57.6                                     30      5.0      1.25    0.86  0.14  71.7                                     30      5.0      1.67    0.86  0.14  85.0                                     ______________________________________                                         (1) Maximum possible yield, corrected for assay, assumed to be 1.0 mole o     DCP.                                                                     

At a fixed temperature and time, the yield of peroxide is controlled bythe amount of hydroperoxide present. The yield is benefited by having anexcess of the hydroperoxide present in the feed and this is especiallyevident when operating at the lower temperatures.

EXAMPLE 8 Effect of Reaction Time on Peroxide Yield

The effect of reaction time on the yield of dicumyl peroxide (DCP) isdemonstrated by a series of runs where in each series the temperatureand proportion of cumene hydroperoxide (CHP), α-methylstyrene (MeS), andcumyl chloride (CX) was fixed. A number of series was carried out at 40°C. using different proportions in each series. Another series wascarried out at 30° C. Each run in each series was carried out accordingto the procedure of Example 1. The results of these runs are set outbelow.

    ______________________________________                                        Temp  CHP    MeS    CX    DCP % Yield at Hours (1)                            ° C                                                                          mole   mole   mole  1.   2.5   5.   7.5                                 ______________________________________                                        40    1.0    0.93   0.07  --   26.5  --   --                                  40    1.0    0.86   0.14  37.6 54.8  60.0 55.6                                40    1.0    0.72   0.28  --   59.4  55.8 --                                  40    1.0    0.59   0.41  28.6 48.5  --   --                                  30    1.0    0.86   0.14  --   38.1  55.7 61.5 (2)                            ______________________________________                                         (1) Based on cumyl hydroperoxide, corrected for assay.                        (2) At 10 hours, the yield of DCP was 60.8%.                             

At a given set of operating conditions, the yield of peroxide isincreased with increasing time of reaction. However, at each set ofconditions, prolonged time results in a decrease in yield -- undoubtedlybecause of decomposition of the peroxide product, as the data showlonger times are permissible at the lower temperature of reaction.

EXAMPLE 9 Effect of Reaction Temperature on Peroxide Yield

The effect of reaction temperature on the yield of dicumyl peroxide(DCP) is demonstrated by a series of runs where in each series theproportion of cumene hydroperoxide (CHP), α-methylstyrene (MeS), andcumyl chloride (CX) and the time of reaction were fixed. A number ofseries was carried out with each run in each series being carried outaccording to the procedure of Example 1. The results of these runs areset out below.

    ______________________________________                                        Time   CHP    MeS     CX    DCP % Yield at Temp. ° C (1)               Hours  mole   mole    mole  30   40    50    60                               ______________________________________                                        2.5    1.0    0.86    0.14  38.1 54.8  58.2  48.3                             2.5    1.0    0.72    0.28  52.6 59.4  55.3  --                               5.0    1.0    0.86    0.14  55.7 59.5  45.0  --                               ______________________________________                                         (1) Maximum possible yield of peroxide, corrected for assay. assumed to b     1.0 mole of DCP.                                                         

At a given set of operating conditions, the yield of peroxide isincreased with increasing temperature but only to a particular optimumtemperature. Thereafter, the yield decreases with increasing temperature-- undoubtedly because of the decomposition of the peroxide product. Itis evident from Examples 8 and 9 that there is an optimumtime-temperature relation at each proportion of the feed charged to thereactor which produces a maximum yield of peroxide product. In general,the best yields are obtained, at a given feed proportion, by associatingthe higher temperatures with the shorter times. However, these examplesshow that it is a reasonably simple matter to determine the optimumconditions for a given feed.

Test 10. Dicumyl Peroxide by direct reaction of hydroperoxide and cumylchloride.

A 100 ml. round-bottom flask was equipped with thermometer, mechanicalstirrer, addition funnel and vacuum take-off. To the flask was charged27.8 g. (0.15 m.) of 82% cumene hydroperoxide. The vacuum take-off wasconnected to a manometer and a water pump; the pressure in the flask wasreduced to 0.02 atmosphere. The purpose of operating under reducedpressure was to remove hydrogen chloride as soon as it was formed in thereaction.

To the addition funnel was charged 23.2 g. (0.15 m.) of cumyl chloride.The reaction flask was surrounded by a water bath. Dropwise addition ofcumyl chloride was begun. The reaction was very exothermic and a longaddition time (3 hours) was required. The reaction mixture in the flaskbecame black. After being stirred for an additional 1.5 hours underreduced pressure, the reaction mixture (with a strong phenolic odor) wastransferred to a separatory funnel; it was washed with 200 ml. of 20%sodium hydroxide solution then with 100 ml. portion of water untilneutral. The dried (magnesium sulfate) product mixture was filtered andstripped in vacuo. The residue (9.4 g.) was very dark and contained only0.17% active oxygen. The active oxygen content of dicumyl peroxide is5.94%. It is probable that no dicumyl peroxide was formed in thisprocedure.

EXAMPLE 11 Dicumyl Peroxide -- Purification Procedures

A. High temperature vacuum stripping

A mixture of 36.4 g. (0.2 m.) of 83.5% cumene hydroperoxide, 5 g.(0.0325 m.) of cumyl chloride and 22.4 g. (0.19 m.) of α-methylstyrenewas stirred for 21/2 hours at 40° C. The reaction mixture was washedwith 50 ml. of water, four 50 ml. portions of 10% potassium hydroxidesolution, 50 ml. of water and finally saturated sodium chloridesolution. The organic layer was dried over sodium sulfate and filtered.The filtrate was then heated gradually to 85°-90° C. at 1 mm. pressure.The product was distilled under 1 mm. of pressure for 90 minutes at85°-90° C. The amber residue, weighing 36.1 g., was allowed to cool toroom temperature; it spontaneously crystallized on standing overnight.The product assayed 85.5% (corrected yield 57.2%) and contained 5.9%hydroperoxide. The product was decolorized by treatment with charcoal inmethanol and recrystallization from methanol.

The average assay for 13 dicumyl peroxide preparations using hightemperature vacuum stripping was 79.0 ± 8.1% and average hydroperoxidecontent was 4.1 ± 0.3%.

B. Liquid Water Vaporization

Another run was carried out under conditions identical to thosedescribed in A above except that after washing with saturated sodiumchloride, the wet crude product was mixed with 300 ml. of water anddistilled at 100 mm. pressure until no further oil came over in thedistillate. The pot residue was cooled by dumping in 50 g. of ice; thedicumyl peroxide spontaneously crystallized as colorless needles. Thedicumyl peroxide was filtered off under vacuum, washed with water andthen allowed to air dry. The colorless crystalline product weighed 34 g.and assayed 94.3% (corrected yield 59.4%) and contained 0.5%hydroperoxide. No further purification was necessary.

The average assay for 23 dicumyl peroxide preparations using the liquidwater vaporation procedure was 95.6 ± 2.0% and average hydroperoxidecontent was 1.45 ± 0.8%.

EXAMPLE 12 t-Butyl Cumyl Peroxide -- Comparison of Cumyl chloride andsulfuric acid preparation and purification procedure

A. Sulfuric Acid Route

Into a jacketed reactor was charged 48.3 g. (0.5 m.) of 93.2% t-butylhydroperoxide. The reaction temperature was maintained at 0° C. bycirculating cold brine through the reactor jacket, while 50 g. of 70%sulfuric acid was slowly added to the hydroperoxide. Then 70.8 g. (0.6m.) of α-methylstyrene was added dropwise over a 30 minute period afterwhich the reaction product mixture was stirred for 3 hours at 0°. Thereaction product mixture was then washed with 100 ml. of water, 100 ml.of 10% potassium hydroxide solution and finally with 100 ml. portions ofwater until neutral. The organic layer was separated, dried (magnesiumsulfate), filtered and stripped in vacuo at 1-3 mm. at ambienttemperature for 2 hours. The residue (73.0 g.) assayed 72.1% t-butylcumyl peroxide by vapor phase chromatography. The yield was 50.7%.

The crude product was distilled at 0.05 mm. through a Vigreux column;the cut boiling at 47°-50° was redistilled and a heart cut taken at45°-47°. This heart cut assayed 92.7%; it darkened on standing.

A series of ten runs were carried out under varying conditions of time,temperature and concentration of acid. The yield ranged from 5.5% to50.7% and assays from 13.2% to 73.2%.

B. Cumyl Chloride Route

A mixture of 126 g. (1.2 m.) of 85.8% t-butyl hydroperoxide, 101.5 g.(0.86 m.) of α-methylstyrene and 21.6 g. (0.14 m.) of cumyl chloride wasstirred for 5 hours at 30 ± 2° C. The reaction mixture was washed (15minutes) with two 50 ml. portions of 10% potassium hydroxide, then withsix 50 ml. portions of saturated sodium chloride solution. The organiclayer (197.3 g.) contained 79.8% of t-butyl cumyl peroxide. The yieldwas 75.7%.

The crude peroxide was purified by the liquid water vaporizationprocedure of Example 11. The purified peroxide assayed 89.9%; itremained colorless in storage at room temperature.

EXAMPLE 13 Crosslinking of Polyethylene

The peroxide (usually 0.01 equivalents of active oxygen per 100 g. ofpolyethylene) was dry blended with finely divided polyethylene"Microthene"™ on a ball mill. The peroxide-containing polyethylene wasthen moulded into 5" × 5" × 0.07 plaques which were then cured in aplaten press at a ram pressure of 20,000 psi. for 30 minutes at thetemperatures specified. The "percent crosslinked" was determined byextracting the uncrosslinked portion with xylene at 80° C. The curingresults are set out below.

    ______________________________________                                                           % Crosslinked -at Cure Temp. (° F)                  Peroxide             320°                                                                           340°                                                                           375°                              ______________________________________                                        t-Butyl cumyl peroxide                                                                             94.0    95.1    95.2                                     t-Butyl p-methylcumyl peroxide                                                                     88.6    90.3    89.5                                     t-Butyl p-isopropylcumyl peroxide                                                                  84.6    85.8    85.5                                     t-Butyl p-t-butylcumyl peroxide                                                                    92.6    94.0    93.7                                     ______________________________________                                    

EXAMPLE 14 Crosslinking of Polyethylene

The peroxide (usually 0.01 equivalents of active oxygen per 100 g. ofpolyethylene) was milled into DYNH-1™, a grade of low-densitypolyethylene on a two-roll mill. The milled sheet was cut into plaquesand cured in a platen press at a ram pressure of 20,000 psi for 30minutes at the temperatures below. The "Percent crosslinked" wasdetermined by extracting the uncrosslinked portion with xylene at 80° C.The results are set out below.

    ______________________________________                                                           % Crosslinked at                                                              Cure Temp. (° F)                                    Peroxide             320°                                                                           340°                                                                           375°                              ______________________________________                                        Dicumyl peroxide     89.5    89.8    89.7                                     p-Methylcumyl cumyl peroxide                                                                       83.6    83.1    83.0                                     p-Isopropylcumyl cumyl peroxide                                                                    83.0    83.2    82.9                                     p-t-Butylcumyl cumyl peroxide                                                                      87.7    87.8    87.2                                     p-chlorocumyl cumyl peroxide                                                                       85.9    85.6    85.0                                     1,4-bis[α(t-butylperoxy)                                                isopropyl]benzene    89.1    91.9    91.3                                     1,3,5-tris[α-(t-butylperoxy)                                            isopropyl]benzene    89.5    91.6    91.2                                     4-[α-(t-Butylperoxy)isopropyl]                                          α,α,α',α'-tetramethylphthalan                                              87.1    89.3    89.1                                     2,5-Bis(cumylperoxy)-2,5-dimethyl-                                            hexane               85.0    85.2    84.2                                     2,5-Bis(cumylperoxy)-2,5-dimethyl-                                            hexyne-3             81.0    86.9    88.1                                     2-[α-(t-butylperoxy)isopropyl]-                                         naphthalene          87.6    89.2    89.2                                     2-[α-(t-butylperoxy)isopropyl]                                          naphthalene          79.8    79.4    78.8                                     1,3-Bis[α-(t-butylperoxy)ispropyl]                                      benzene              89.3    91.7    91.4                                     2-Fluorocumyl cumyl peroxide                                                                       89.1    89.6    88.8                                     ______________________________________                                    

Thus, having described the invention, what is claimed is:
 1. A processfor preparing peroxides which process consists essentially of:(1)reacting an olefin, a reactive organic halide and an organichydroperoxide, under substantially anhydrous conditions, at atemperature in the range of about 0°-60° C., where (2) said olefin hasthe formula: ##STR33## where (a) y is an integer equal to 1, 2 or 3;(b)R¹ is a phenyl or naphthalene group; (c) R² and R³ are each H, alkyl,cycloalkyl, phenyl, or a corresponding halo substituted radical, or R²and R³ join with the common carbon atom to which they are attached orwith ##STR34## to form a cyclic group; (d) R⁴ is alkyl, cycloalkyl,phenyl, or a corresponding halo substituted radical; and(e) when R¹ issubstituted on more than one ring carbon atom, not more than one ringcarbon atom ortho to a ##STR35## group can be joined to a substituentgroup; (3) said reactive organic halide has the formula: ##STR36## whereX is Br or Cl; (4) said organic hydroperoxide has the formula:

    R.sup.5 (-- OOH).sub.y

where R⁵ is an aliphatic or cycloaliphatic hydrocarbon radical, or acorresponding halo substituted radical; (5) the mole ratio ofhydroperoxide groups in said organic hydroperoxide charged to theethylenic bonds in said olefin charged is 2-1.1 to 1; and (6) saidhalide is charged in an amount of about 2-20 mole percent based onolefin charged.
 2. The process of claim 1 wherein the reaction time isin the range of about 1-12 hours, the longer times being associated withthe lower temperatures.
 3. The process of claim 2 wherein said halide ischarged in an amount of about 10-20 mole percent based on olefincharged.
 4. The process of claim 3 wherein one peroxy oxygen of --OOH isjoined to a tertiary carbon atom in R⁵.
 5. The process of claim 3wherein R⁵ is lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl,cycloalkenyl, cycloalkyl-lower alkyl, aralkyl, aralkenyl, thecorresponding di and tri-valent radicals, or the corresponding halosubstituted radicals.
 6. The process of claim 5 wherein saidhydroperoxide is t-butyl hydroperoxide.
 7. The process of claim 5wherein said hydroperoxide is cumene-hydroperoxide.
 8. The process ofclaim 5 wherein said hydroperoxide is2,5-dimethyl-2,5-dihydroperoxyhexyne-3.
 9. The process of claim 3wherein said olefin is α-lower alkyl vinylbenzene.
 10. The process ofclaim 9 wherein said vinylbenzene is α-methylstyrene.
 11. The process ofclaim 9 wherein halide corresponds to said vinylbenzene.
 12. The processof claim 11 wherein said halide is cumyl chloride.
 13. The process ofclaim 3 wherein said temperature range is about 20°-50° C.
 14. Theprocess of preparing cumyl peroxide which consists essentially ofreacting at about 30° C. for about 5 hours cumene hydroperoxide,α-methylstyrene and cumyl chloride, which compounds has been charged tothe reaction zone in a mole ratio of 1.25; 0.86; 0.14 and treating thereaction product mixture with aqueous alkali metal hydroxide to removecumyl chloride and cumyl hydroperoxide to obtain a product mixtureincluding dicumyl peroxide.